Activity-based analysis of potentiometric pH titrations.

The discrepancy between concentrations and activities is a predicament well known to the analytical chemist. Because of the difficulty of determining activity coefficients, the standard technique for quantitative equilibrium studies is to work under a particular 'constant ionic strength' by adding an excess of an inert salt. Under such conditions, activity coefficients are approximately constant and can be taken into the equilibrium constants which are defined for the chosen ionic strength (I). Here we propose a fundamentally different approach. Throughout the numerical analysis of the titration data, activity coefficients for all individual species are approximated by well-known equations based on the work of Debye-Hückel. The computational analysis of the measurements strictly obeys the law of mass conservation and obeys the law of mass action only approximately. The main novelty is that now the addition of inert salts is no longer required and measurements are done at minimal I. Consequently, the thermodynamic equilibrium constants are now determined much more robustly based on experiments taken at low I. The approach has been tested and validated with the two very well investigated 3-protic phosphoric and citric acids. In summary: the technique of artificially keeping ionic strength constant has been replaced by improved computational analysis.

Comprehensive study of the hydration and dehydration reactions of carbon dioxide in aqueous solution.

The reversible interactions of dissolved CO(2) with H(2)O and OH(-) to form H(2)CO(3) and HCO(3)(-) in aqueous solution have been investigated using spectrophotometric stopped-flow measurements. The progress of the reactions was monitored via indicators coupled to the pH changes during the reactions. The study, involving global analysis of the complete data set, spanned the temperature range 6.6-42.8 degrees C and resulted in the evaluation of all rate and equilibrium constants as well as activation parameters for the kinetic data and the reaction enthalpies and entropies for the equilibrium constants.

Tutorial: the modelling of chemical processes.

The modelling of chemical processes entails the computation of the concentration profiles of all reaction species as a function of the reaction time. The basis for the calculations is the system of differential equations (ODE's) that is defined by the reaction mechanism. Most textbooks on chemical kinetics concentrate on those few reaction mechanisms that lead to ODE's with explicit solutions. In this tutorial, we demonstrate that numerical integration is a viable alternative, that it can be applied to any mechanism, and that it is easy to do so. Matlab example programs illustrate the concepts and they allow the reader to explore the effects of changing conditions such as initial concentrations or rate constants etc. Example reaction mechanisms include a zero-th order enzymatic reaction and reactions at non-constant temperature and pH.

Kinetics and mechanism of carbamate formation from CO2(aq), carbonate species, and monoethanolamine in aqueous solution.

Removal of carbon dioxide from fossil-based power generation is a potentially useful technique for the reduction of greenhouse gas emissions. Reversible interaction with aqueous amine solutions is most promising. In this process, the formation of carbamates is an important reaction of carbon dioxide. In this contribution, a detailed molecular reaction mechanism for the carbamate formation between MEA (monoethanolamine) and dissolved CO(2) as well as carbonate species in aqueous solution is presented. There are three parallel, reversible reactions of the free amine with CO(2), carbonic acid, and the bicarbonate ion; the relative importance of the three paths is strongly pH dependent. Kinetic and equilibrium measurements are based on (1)H NMR and stopped-flow measurements with rate constants, equilibrium constants, and protonation constants being reported.

Complexation kinetics of copper(II) and nickel(II) with macrocycles: identification of an outer-sphere chelate effect.

Ligand-protonation constants and complexation kinetics of differently protonated forms of 10-methyl-1,4,8,12-tetraazacyclopentadecan-10-amine, 1,4,8,12-tetraazacyclopentadecane, and 1,4,8,12-tetraazacyclopentadecan-10-carboxylic acid with Cu(II) and Ni(II) in aqueous solution have been determined. These results are combined with a wide range of published complexation rate constants of partially protonated macrocyclic ligands with the same metal ions. Insight is gained into the electrostatic effects and the outer-sphere interaction of partially protonated ligands with aquated metal ions. An outer-sphere chelate effect has been ascertained.

Characterization of novel vanadium(III)/acetate clusters formed in aqueous solution.

We report the first structures of simple acetate complexes of vanadium(III) formed in aqueous solution. Paramagnetic (1)H NMR spectroscopy titration experiments indicate the formation of two major V(III)/acetate complexes in acidic aqueous solution for acetate/V(III) < or =4, pD 3.50. A novel tetranuclear cluster and a trinuclear cluster have been characterized by X-ray diffraction studies. Mass spectrometry measurements show these clusters retain their integrity in solution.